Epoxy resins from halogen-substituted, unsaturated alcohols



United States Patent This is a division of application Ser. No. 157,270,filed Dec. 5, 1961, now Patent No. 3,324,187.

The present invention relates to new and useful halogensubstituted,unsaturated alcohols and to a process for their manufacture. Moreparticularly, the invention relates to new and useful,fluorine-substituted, olefinic alcohols and r to a process for thepreparation of said alcohols.

It has been proposed to prepare unsaturated, fluorinated alcohols bytreatment of hexafiuoroacetone with acetylene magnesium halides.Processes of this type, commonly known in the art as Grignard reactions,are applicable for the preparation of a variety of halogenated,unsaturated alcohols by interaction of halogenated ketones or aldehydeswith organomagnesium compounds. These processes are undesirable from acommercial standpoint, however, in view of the necessary utilization ofrelatively expensive Grignard reagents.

We have now discovered that fluorine-substituted, olefinie alcohols maybe economically prepared in high yield by intimately admixing undersubstantially anhydrous conditions a fluorine-substituted,perhalogenated acetone with an a-olefinic compound having at least threecarbon atoms in the olefinic chain.

Preferred perhalogenated acetones possess the general formula wherein Xis a member selected from the group consisting of fluorine and chlorineand the total number of chlorine atoms ranges from 0 to 4.

Illustrative examples of perhalogenated acetones which may be employedinclude the following compounds ll ClF2CCC F2011,3-dielilorod,1,3,3-tetrafiuoroacetone II F ono-o-o 01211,1,3,3-tetrachlorod,3-difluor0acetone ii C13CCC F31,1,1-t1'iflnor0-3,3,3-trichloroacetone Preferred a-olefinic compoundspossess the general formula CH-=CH2 wherein R is a member selected fromthe group consist- 3,372,152 Patented Mar. 5, 1968 ing of alkyl,cycloalkyl, aryl, aralkyl, alkoxy and aryloxy and R and R are like orunlike members selected from the group consisting of hydrogen, alkyl,cycloalkyl, aryl, aralkyl, alkoxy, aryloxy, halogen, amide, acyl,carboalkoxy, vinyl and allyl.

Specifically, R may be methyl, ethyl, propyl, butyl, cyclohexyl, phenyl,naphthyl, benzyl, methoxy, ethoxy, propoxy and phenoxy: R and R may behydrogen, methyl, ethyl, propyl, butyl, phenyl, naphthyl, benzyl,cyclohexyl, methoxy, ethoxy, propoxy, butoxy, phenoxy, chlorine,bromine, fluorine, iodine, acetamide, acetyl, propionyl, canbomethoxy,cauboethoxy, carbopropoxy, carbobutoxy, vinyl and allyl. These radicals,however, are merely illustrative.

Among the aforesaid substituent groups, those derived from hydrocarbonmolecules may, in themselves, possess a variety of additional secondarysubstituents. The secondary substituents may be any one of thesubstituent groups, R R and R defined hereinabove. In addition, othersecondary substituents may be present provided that the substituents donot appear nearer to the terminal olefinic linkage than on a carbon atomin a position beta to said linkage. Members of this last-named class ofsubstituents may 'be selected from the group consisting of amino,hydroxy, dialkylamino, diarylamino, dicycloalkylamino anddiaralkylamino.

Alternatively, u-olefinic compounds of the above formula wherein R ishydrogen or acyloxy (e.g. acetoxy) may be employed. In this instance, Rand R may be like or unlike members selected from the group consistingof hydrogen, alkyl, cycloalkyl, aryl, aralkyl and alkoxy. In addition, Rand R may possess the secondary substituents described above.

Illustrative examples of a-olefinic compounds suitable for the processof our invention are given below.

0 H3 C H: 0 H2 propylene CH3CHCH=OH2 l-butene O=CH isobutylene C a( 2)1=CH2 l-decene C H2=C HC H20 H2C 11:01},

1,5-hexadiene Ii (i) C 0 Ha 0 H3 C=OH2 2-acetoxypropene C H2: C 0 H2 Cl2-methyl-3-chloropr0pene 2-benzylpropene a-methylstyrene G CH3 CH3lirnonene CH3 H2 2-cyclohexylpropene 4-isopropenylmethylbenzoate CHzNOzCH CHz-C=CHz 2mitromethyl-1-butene C H3 C Hz C: C H2 Z-methoxy-l-bn teneAlthough we do not wish to be bound by any particular theory, it appearsthat an alkene compound possessing a terminal olefinic linkage isnecessary for a facile reaction rate in our process. The process may bebest illustrated by reference to Equation 1, wherein the formation ofthe fluorine-substituted olefinic alcohols features a migration andretention of the olefinic linkage originally present in the molecule,

In those alkene compounds which possess two terminal olefinic linkages,it is possible to interact perhalogenated acetones therewith to producea dihydric, fluorine-substituted olefinic alcohol. Such a process may beillustrated by Equation 3, wherein 1,5-hexadiene is employed as theolefinic compound and X is a halogen as defined above.

The process of this invention must be conducted under substantiallyanhydrous conditions. The presence of water or any electron-donatingspecies, such as ammonia or amines or alcohols, will tend to interactwith an equivalent number of perhalogenated acetone molecules to formcomplexes with the molecules, rendering said molecules inactive.

The most convenient manner for excluding extraneous inhibitors is byadmixing the perhalogenated acetone with concentrated sulfuric acid orother suitable drying agent, and distilling the acetone therefrom, underre duced pressures, if necessary. However, any procedure readilyavailable to those skilled in the art may be employed.

In order to produce a monohydric fluorine-substituted olefinic alcoholfrom a monoolefinic compound which will not form a dihydric alcohol, amol ratio of perhalogenated acetone to monoolefinic compound of at least1:1 is preferred. However, an excess of either reactant may be useddepending on the value of the reactant and its ease of separation. Theproduction of a dihydric olefinic alcohol from a monoolefinic compoundcapable of producing the same requires that the ratio of perhalogenatedacetone to monoolefinic compound be at least 2: 1. The degree of excessin either instance is not critical and may be as large as economicconsiderations will permit. Preferably, however, not more than about 3times the theoretical mol ratio is used in either case. Hence, forproduction of a monohydric alcohol where formation of no dihydricalcohol is possible, a mol ratio of perhalogenated acetone tomonoolefinic compound ranging from 1:1 to about 3:1 is generallyemployed. For production of a dihydric alcohol from a monoolefiniccompound capable of forming the same, the mol ratio may range from 2:1to about 6:1. In those instances where it is desired to produce amonohydric alcohol from a diolefinic compound or a monoolefinic compoundwhich will form a dihydric alcohol, the converse ratio may be employed,i.e., a mol ratio of perhalogenated acetone to olefinic compound lessthan 1:1, the ratio being dependent upon the relative reactivity of theolefinic groups but usually ranging from about 0.2 to 0.9:1. Forproduction of a dihydric alcohol from a diolefinic compound, a mol ratioof perhalogenated acetone to diolefinic compound ranging from 2:1 toabout 6:1 is generally used.

Care must be exercised when employing a-olefinic compounds containinghydroxy, amino and the like groups in the olefinic molecule inasmuch asthe hydroxy and amino moiety of such olefinic compounds may function toinactivate a portion of the perhalogenated acetone present in thereaction mixture. The undesirable reduction in yield predicated by saiddeactivation may be circumvented by utilization of an excess of theperhalogenated acetone, and, at termination of the process, by utilizinga quantity of mineral acid to rupture the complexes thus formed. Theunreacted, perhalogenated acetone may then be separated from thecondensation products in the reaction mixture.

Although the preferred temperature range for the reaction is from about20 to 100 C., temperature as low as C. and as high as 250 C. areapplicable.

In the preferred mode of operation, the process is performed in theabsence of any solvent, but, if control of reaction rate is desired,inert organic solvents which will not appreciably inactivate thecarbonyl group of the perhalogenated acetones may be used. Suitablesolvents include aromatic and aliphatic hydrocarbons such as tolu ene,benzene, xylene, pentane, hexane, and petroleum ether, as well as etherssuch as tetrahydrofuran and nitriles such as acetonitrile. The presenceof such solvents acts to slow down the reaction rate of the process byvirtue of dilution and complex formation of the solvent with theperhalogenated acetone.

The dihydric, fluorine-substituted, olefinic alcohols of our inventionare admirably suitable for the production of epoxy resins as describedin Example 10 hereinbelow. The resins may be used as adhesives, asindicated by their high resistance to abrasion, their flexibility, andtheir resistance to a variety of chemical solvents. Preferred dihydricalcohols may be represented by following general wherein R is a memberselected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl,alkoxy and aryloxy, R is a member selected from the group consisting ofhydrogen, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, halo gen, amide,acyl, 'carboalkoxy, vinyl and allyl, X is a member selected from thegroup consisting of chlorine and fluorine, the total number of chlorinerepresented by X ranging from O to 4, m is an integer ranging from to 1,n is an integer ranging from 0 to 20 and p is an integer ranging from 0to 1.

Alternatively, R may be hydrogen or acyloxy, in which case R is a memberselected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl,aralkyl and alkoxy.

The monohydric alcohols of the invention are useful as plasticizers forresinous compositions. These alcohols may *be esterified and the highlyhalogenated, inert esters produced therefrom employed for thestabilization of resinous materials against the decompositional efiectsof heat.

The following specific examples will further illustrate the invention.In the examples, parts are by weight and temperatures are in degreescentigrade.

Example 1 Isobutylene (5.6 parts) was distilled under mm. Hg pressureinto a thoroughly dried ampule. In a similar manner, hexafluoroacetone(14.2 parts) was added, and the ampule was brought to 0 in an ice bathand sealed. The reaction mixture was maintained at 35-40 for 12 hours,at the end of which time the ampule was opened. A precipitate (18 parts)appeared which was removed by filtration. The filtrate was collected anddistilled at 113 under 758 mm. Hg pressure to yield 1,1,1-trifluoro-2-hydroxy-2-trifluoromethyl 4 methyl-4-pentene (11.8 parts) of thestructure The product was obtained in a yield of 100% of theoretical andpossessed a refractive index, n =1.3503, and the following elementalanalysis:

Theoretical: carbon, 37.84% hydrogen, 3.62%. Found: carbon, 37.64%;hydrogen, 3.69%.

Example 2 The procedure of Example 1 was repeated utilizing 14.0 partsof isobutylene and 83.0 parts of hexafluoroacetone. After standing for12 hours at 25 in a dry, sealed ampule, the ampule was opened. A solidproduct was obtained which was recrystallized from chloroform. Theproduct,

having the following structural formula, melted at 14-6- 147". l

The product exhibited an infrared spectra wherein the presence ofolefinic double bonds was indicated by absorption at 10.35 microns,carbon-hydroxy absorption at 3.0 microns and carbon-fiuorine absorptionat 8.1-8.4 microns.

Example 3 l-butene (13.4 parts) was admixed with hexafluoroacetone (21.5parts) in the manner described in Example 1. The ampule was permitted tostand at room temperature for 12 hours, and was then cooled to 0 andopened. A liquid residue was obtained (15 parts) which distilled at65.5-66.5" under 110 mm. Hg pressure to yield a clear distillate of 1, l1-trifluoro-2-hydroxy-2-trifluoromethyl-4- hexene possessing arefractive index, n =l.3475, and the following structural formula 0 FCHaOH=CHCH2-OH a. The product had the following elemental analysis:

Theoretical: carbon, 37.84%; hydrogen, 3.62%. Found: carbon, 37.87%;hydrogen, 4.10%.

Example 4 In a manner similar to that described in Example 1, carefullydried 2-acetoxypropene (10.1 parts) was admixed with hexafluoroacetone(11.4 parts), sealed in an ampule, and heated first at 25 for 56 hours,then at 60 for 15 hours and finally at for 38 hours. The ampule wascooled to 0 in an ice bath and opened. The liquid reaction mixture waswashed with water, and then dried over magnesium sulfate. The compoundwhich was isolated, 1,1,1-trifluoro-2 hydroxy 2 trifiuoromethyl 4-acetoxy-4-pentene, possessed a refractive index.

and the following structural formula CIKECHS CF; oH2=o-oH2 3-o11' Theinfrared spectra of the product had absorption bands at 3.31 and 5.99microns indicative of olefinic bonds, a band at 2.95 microns indicatingthe presence of a hydroxy group, a band at 8 microns indicative of thepressence of a carbon-fluorine bond and bands at 5.83 and 8.0 micronsindicating the presence of a carbonyl group.

Example 6 In a manner similar to that described in Example 1,a-rnethylstyrene 11.8 parts) was admixed with1,3-dichloro-l,1,3,3-tetrafluoroacetone (19.9 parts) and permitted tostand for 60' hours at 60. The viscous reaction 7 mixture therebyobtained was distilled at 8689 under 0.6 mm. Hg pressure to yield1,1-difluoro1-chloro-2-difluorochloromethyl-2-hydroxy-4-phenyl-4 pentenewhich possessed a refractive index n =1.4925, and the followingstructural formula Example 7 The process of Example 6 was repeatedemploying 9.9 parts of a-methylstyrene and 44.7 parts of 1,3-dichloro-1,1,3,3-tetrafluroacetone. The product had the following structuralformula The product exhibited the following elemental analysis:

Theoretical: carbon, 34.9%; hydrogen, 1.94%; chlorine, 27.5%. Found:carbon, 35.19%; hydrogen, 2.50%; chlorine, 27.0%.

In addition, the product exhibited infrared spectra showing absorptionbands at 6.33 and 6.68 microns indicative of the presence of a benzenoidnucleus, bands at 13.05 and 14.35 microns indicating a mono-substitutedbenzenoid nucleus, absorption bands from 8.4 to 8.7 microns indicativeof a carbon-fluorine bond, a band at 6.09 microns indicative of anolefinic linkage and a band at 2.99 microns indicative of the presenceof a hydroxy group.

Example 8 In a manner similar to that described in Example 1,1,5-hexadiene (8.2 parts) was admixed with 1,3-dichloro-1,1,3,3-tetrafluoroacetone (19.9 parts) and maintained in a sealedampule for 24 hours at 100. The mixture was then distilled on a spinningband column at 43-44 under 0.4 mm. Hg pressure to yield1,1-difiuoro-1-chloro- 2-hydroxy 2 difiuorochloromethyl-3,6-heptadiene(25.3 parts) of the following structural formula The product possessed arefractive index, n =1.4395, and had the following elemental analysis:

Theoretical: carbon, 38.4%; hydrogen, 3.58%. Found: carbon, 38.01%;hydrogen, 3.78%.

Infrared spectra of the product showed the presence of an absorptionband at 2.85 microns indicative of a hydroxy group, a band from 8.4 to8.8 microns indicating a carbon-fluorine bond and a band at 3.25 and 6.1microns indicative of an olefinic linkage.

Example 9 The procedure of Example 8 was repeated with 4.1 parts of1,5-hexadiene and 29.9 parts of 1,3-.dichloro-1,1,3,3-tetrafluoroacetone. A yield of 34.3 parts of 1,1,8,8-

tetra(difiuorochloromethyl) 1,8-dihydroxy-3,5-octadiene of the followingstructural formula was obtained:

The product possessed a refractive index, n =1.4574, and had thefollowing elemental analysis:

Theoretical: carbon, 30.00%; hydrogen, 2.08%; fluorine, 29.4%. Found:carbon, 30.45%; hydrogen, 2.20%; fluorine, 28.56%.

Infrared spectra of the product showed a hydroxy band at a wave lengthof 2.83 microns, an absorption band at 8.4-8.75 microns indicative of acarbon-fiuorine bond, an absorption band at 3.4 and 6.94 micronsindicating. the presence of a methylene group and an absorption band at3.29 and 6.01 microns indicating the presence of olefinic groups.

Example 10 PREPARATION OF EPOXY RESIN The dihydric alcohol produced byExample 2 (19.4 parts) was admixed in a resin pot with epichlorohydrin(46.25 parts) and distilled water (0.5 part). The resin pot was equippedwith a condenser, a thermowell, a mechanical stirrer and a reagent feedopening. The reaction mixture was agitated and heated at 60 for 30minutes, at the end of which 1.0 part of sodium hydroxide was addedthereto. The temperature was increased to 75 and maintained at thattemperature for about 15 minutes, then dropped to 60 at which timeadditional sodium hydroxide (1.0 part) was added. This procedure wasrepeated two more times until a total of about 4.2 parts of sodiumhydroxide had been added to the reaction mixture. The temperature ofsaid mixture was then raised to 95 and maintained at that temperaturefor one hour. At the end of this time, unreacted epichlorohydrin andwater were removed from the reaction mixture by distillation at 150under mm. Hg pressure, and the residue was permitted to cool to about25. Acetone (25 parts) was then added to the residue and insoluble saltswere removed from the resulting mixture by filtration. The filtrate wascollected and acetone was removed therefrom by distillation at 120 under90 mm. Hg pressure. A clear, water-white liquid was obtained in 60%yield of theoretical based on the monomer added to the initial reactionmixture. The material was an epoxy resin possessing an epoxideequivalent of 298. I

This resin was readily transformed into a film by admixing the resin (5parts) with diethylene triamine (0.35 part) and acetone (20 parts). Acured film was prepared on a bonderized steel panel by heating the abovemixture at for one hour. The product obtained possessed the filmproperties illustrated in Table I.

TABLE I Physical properties:

1 ASTM D522-41.

A V-shaped cut was made in the film, and a strip of cellophane tape waspressed down on the film and abruptly ripped away to see if it removedany of the film. 19 i90rganic Coating Technology, J. Wiley & Sons, page0 12,

While the above describes the preferred embodiments of this invention,it will be understood that departures may be made therefrom within thescope of the appended claims.

9 We claim: 1. A fluorine-substituted, epoxy resin prepared by theinteraction of epichlorohydrin with a dihydric, fluorinesubstituted,olefinic alcohol having the general formula wherein R is a memberselected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl,alkoxy and aryloxy, R is a member selected from the group consisting ofhydrogen, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, halogen, amide,acyl, carboalkoxy, vinyl and allyl, X is a member selected from thegroup consisting of chlorine and fluorine, the total number of chlorineatoms represented by X ranging from to 4, m is an integer ranging from 0to 1, n is an integer ranging from 0 to 20 and p is an integer rangingfrom 0 to 1.

2. A fluorine-substituted, epoxy resin prepared by the interaction ofepichlorohydrin with a dihydric, fluorinesubstituted, olefinic alcoholhaving the general formula CXa 10 v wherein R is a member selected fromthe group consisting of hydrogen and acyloxy and R is a member selectedfrom the group consisting of hydrogen, alkyl, cycloalkyl, aryl, aralkyland alkoxy, X is a member selected from the group consisting of chlorineand fluorine, the total number of chlorine atoms represented by Xranging from 0 to 4, m is an integer ranging from 0 to 1, n is aninteger ranging from 0 to 20 and p is an integer ranging from 0 to 1.

References Cited UNITED STATES PATENTS 2,490,753 12/ 1949 Hill et a1.260633 X 2,557,639 6/1951 Derr et a] 260 -476 X 2,559,628 7/1951 Joyce260633 2,666,797 1/1954 Husted et a1 260633 2,824,897 2/1958 Wujciak etal. 260633 2,870,101 1/1959 Stewart 260-2 2,914,490 11/1959 Wheelock2602 2,917,469 12/1959 Phillips et a1. 2602 3,140,298 7/1964 England 260-617 3,268,561 8/1966 Peppel 260348 WILLIAM H. SHORT, Primary Examiner.

T. PERTILLA, Assistant Examiner.

1. A FLUORINE-SUBSTITUTED, EPOXY RESIN PREPARED BY THE INTERACTION OFEPICHLOROHYDRIN WITH A DIHYDRIC, FLUORINESUBSTITUTED, OLEFINIC ALCOHOLHAVING THE GENERAL FORMUAL